Levelling agents for and process for colouring a fibrous natural polyamide with reactive dyes

ABSTRACT

A LEVELLING AGENT FOR COLOURING A FIBROUS NATURAL POLYAMIDE WITH A REACTIVE DYE IS CONSTITUTED BY AN ALKOXYLATED AMINE OR AN ADDITION PRODUCT THEREOF WITH A POLYBASIC ACID, OR QUATERNIZATION PRODUCT THEREOF, OR AN ESTERIFICATION PRODUCT THEREOF (ESPECIALLY A SULPHATION PRODUCT), OR AN ETHERIFICATION PRODUCT THEREOF, SAID ALKOXYLATED AMINE BEING SIMILAR TO PREVIOUSLY USED LEVELING AGENTS FOR SIMILAR PURPOSES, EXCEPT THAT THE ALKOXYLATED PORTION CONTAINS BOTH ETHYLENE OXIDE AND PROPYLENE OXIDE GROUPS, BUTYLENE OXIDE GROUPS BEING OPTIONALLY PRESENT IN ADDITION TO SAID ETHYLENE OXIDE AND PROPYLENE OXIDE GROUPS; THE COLOURING MAY BE EFFECTED, E.G., BY DYEING, PADDING OR PRINTING AND THE NATURAL POLYAMIDE IS PREFERABLY WOOL, E.G. IN THE FORM OF YARN OR CLOTH.

United States Patent 3,627,475 LEVELLING AGENTS FOR AND PROCESS FORCOLOURING A FIBROUS NATURAL POLY- AMIDE WITH REACTIVE DYES Hans-PeterBaumann, Basel-Land, Switzerland, assignor to Sandoz Ltd., Basel,Switzerland No Drawing. Filed May 12, 1969, Ser. No. 823,980 Claimspriority, application Switzerland, May 17, 1968, 7,402/68; May 27, 1968,7,959/68; June 12, 1968,

Int. Cl. D0611 3/14 US. Cl. 8-54 10 Claims ABSTRACT OF THE DISCLOSURE Alevelling agent for colouring a fibrous natural polyamide with areactive dye is constituted by an alkoxylated amine or an additionproduct thereof with a polybasic acid, or a quaternization productthereof, or an esterification product thereof (especially a sulphationproduct), or an etherification product thereof, said alkoxylated aminebeing similar to previously used levelling agents for similar purposes,except that the alkoxylated portion contains both ethylene oxide andpropylene oxide groups, butylene oxide groups being optionally presentin addition to said ethylene oxide and propylene oxide groups; thecolouring may be effected, e.g., by dyeing, padding or printing and thenatural polyamide is preferably wool, e.g. in the form of yarn or cloth.

The present invention relates to a process for colouring, e.g. bydyeing, padding or printing, fibrous material of natural polyamides withreactive dyes and to articles resulting from said process.

In the dyeing of wool with reactive dyes it is known to use levellingagents consisting of products obtained by the addition of ethylene oxideor propylene oxide to fatty amines or fatty aminoalkylamines.

It has now been found, in accordance with the invention, that it ispossible to obtain products, which are more effective in the dyeing offibrous material from natural polyamides with reactive dyes than theknown products, by using as levelling agent an addition product to thesaid amines of not only one of the said alkylene oxides but of both ofthem and/or butylene oxide.

The present invention thus provides a process for colouring, e.g. bydyeing, padding or printing, fibrous material of a natural polyamidewith a reactive dye, characterized in that the colouring is effected inthe presence of an alkoxylated amine of the formula or an additionproduct thereof with a polybasic acid, wherein R is a hydrocarbonresidue of a high molecular weight fatty acid,

m is an integer of from 1 to 6,

n is an integer of from 2 to 6,

p is l or 2,

each of r, s and t independently of one another is an integer of from 1to 200, and

Patented Dec. 14, 1971 each of x, y and 2 independently of one anotheris 2,

The compound of the Formula I may be produced by reacting theappropriate alkylene oxides with an amine of the formula each of R, (A),m, n and p has the above significance,

wherein and the resulting compound is acylated with a polybasic acidwhen an acylated product is required.

Examples of suitable amines of the Formula II, in

which p=l, are tallamine, aminopropyltallamine, aminoethyltallamine andalso amines shown in Table 1 given hereinafter under the designation ofAM Index, further dodecyl-, tetradecyl-, cetyl-, stearyl-, oleyl-,arachinyl-, =behenyland lignocerylamine, or polyamines produced byaminoalkylation of the above mentioned amines, for examplealkylaminoethylamines and alkylaminopropylamines.

The addition of the alkylene oxides may be effected according to methodsknown per se, for example in the presence of catalysts, e.g. alkalimetal hydroxides, at ordinary or superatmospheric pressure andtemperatures of from to C.

It is possible to add the alkylene oxides in any desired sequence. Forexample, ethylene oxide may be added first and then propylene oxidetogether with any butylene oxide which may be used, or propylene oxidemay be added first together with any butylene oxide used and only thenethylene oxide or said oxides may be added simultaneously or inalternating manner. When simultaneous addition is effected, it ispossible to use mixtures containing ethylene oxide and propylene oxideand, when applicable, butylene oxide.

The resulting addition products may, furthermore, be quaternized withdimethyl sulphate or similar quaternization agents, for example diethylsulphate, methyl chloride or benzyl chloride, halogen carboxylic acidsor their esters or amides, or esterification may be effected with lowmolecular weight carboxylic acids or preferably, with polybasicinorganic acids, for example with sulphuric acid using a suitablesulphation agent, for example sulphamic acid, or etherification may beeffected with a salt of a halogen carboxylic acid.

The products used in the process of the invention, or their salts,quaternization and/ or acylation products may be added to the dyebath inan amount of 0.01 to 5% based on the goods to be dyed, addition beingpreferably effected before dyeing. Dyeing may be carried out in theusual way and with the help of usual additives at the boilingtemperature or, alternatively, at temperatures of from 50 C. up, e.g. upto 90 C.

The compounds of the Formula I are liquid to pastelike compounds whichare soluble or dispersable in water or dilute acids. By reactive dyesare meant those which contain at least one reactive group, for examplethe ethyleneirnide-, epoxy-, vinyl-, vinyl-sulphonicor acrylic acidgroups, the halogen triazineor halogenpyrimidine groups.

It will be appreciated that the process of the invention may be effectedwith the products of the Formula I above in the form of their ethers,esters, salts or quaternization products and accordingly the use ofthese ethers, esters, salts and quaternization products is included inthe present invention.

In the following examples the temperatures are stated in degreescentigrade and all parts and percentages are by weight.

EXAMPLES 1 to 69 Examples 1-3O (Table 2) show the production ofcompounds of the Formula I wherein 12:1 in tabular form; the method ofproducing the compounds in itself is known, the general conditions beingas indicated above. Table 1 shows the amine starting material used forthe production of the compound I listed in Table 2. In both Table 1 and2 R signifies the alkyl residue of tallow fatty acid, R indicates thealkyl residue of coconut oil fatty acid and R signifies the cetylresidue. In Table 2 the first column, headed Adjuvant shows the numberof the compound of Formula I, the second column shows the startingmaterial amine of the Formula II (i.e. AM index according to Table .I),the third, fourth and fifth columns show the number of mols of alkyleneoxide which were used per mol of amine of the Formula II in order toproduce the Adjuvant.

In manner similar to Table 2, there are listed in Table 3 (Examples3169) compounds of the Formula I in which 12:2, but in this case thereare 8 columns present which give the following information:

Column:

1 No. of adjuvant.

2 Fatty acid reacted with amine of column 3, 3 Amine of column 111.

4 No. of mols of amine of column III reacted with 1 mol of fatty acid.

5] Indicate respectively the number of mols of 6 the various alkyleneoxides added to the 7} reaction product of fatty acid and amine. 8(Remarks) shows any acylation agent and its amount.

TABLE 1 TABLE 2 No. of mols ofl,2-pro- 1,2-bu- Adju- 1 mol of aminepylene Ethylene tylene vant (AMindex) xlde xide oxide Remarks 20 Plus 1mol HOSO Cl. 169 31 10 12 2O 2 Plus 1 mol N HzSOaH. 200 100 8 14 15 1 15 1 2 6 1 Plus 1 mol NHzSOaH. 15 20 Do.

1 1 1 1 1 Do. 25.. RNH(OH3) :i-NHg 3 5 26.-- Same as above 3 15 27 o 105 28. R-NH(OH NH, 10 5 1 29"- R- g 5 3 30 NH(CHg)a-NH1 3 10 3 Plus 1 molH 804.

TABLE 3 No. of mols oi- 1,2- b 1,?- D PY W Adju- 1 mol of fatty acid eneEthenene vant amine oxide oxide oxide Remarks 14 21 14 21 Plus 1.25 molNHzSOaH. 100 100 10 15 2 15 25 2 Plus 2 mol HOSO CI.

52 d0 53 Coconut oil fatty acid.-. 54 Naphthenic acid 55 Stearic acidPlus 1 mol NHaSO H.

1 5 Plus 1.25 mil NHQSOSH- 1 10 Plus 1 mol H PO 2 10 1 15 2 15 1 14 11.2 10 1. 1 14 1. 2 200 PH 0.5 20 DT 1. 1 10 DT l. 1 10 1. 1 14 1. 13 1. 11 42 I; 1 Plus 1 mol NHzSOzH.

TAB LE 3-Goutinucd No. of mols of- 1,2- 1,2- propylbutyl- Adju- 1 mol offatty acid ene Ethenone vant amine Amine Amine oxide oxide oxide Remarks59 Coconut oil fatty acid... PD 1. 1 Plus 1 mol HOSO Cl. 60 Tallow fattyacid DT 1. 1 5 Plus 1 mol NH SOgH. G1 do DT l. 1 62. CnCu-fatty aci DI0. 5 5 Plus 1 mol H 804. 63 Stearic acid- PH 0.33 8 Plus 1 mol N H SOHa.64. do TP 1.1 6 D0. 65 Behem'c acld 1. 5 6 14 1 l. 15 1. 1 14 l 14 InTable 3 the letters in the third column signify the amines as listedbelow Further examples for the production of compounds of the Formula Iwherein p=1 are the following Examples 70 to 90.

EXAMPLE 70 48 parts of ethylene oxide and thereafter 139 parts ofpropylene oxide are added to 36 parts of a commercially available aminemixture having the following composition:

palmityl-aminopropylamine-about 30% stearyl-aminopropylamineabout 30%oleyl-aminopropylamine--about 40% The addition is effected in knownmanner at a temperature of from 120-1 60 C. There results a product a.

EXAMPLE 71 132 parts of ethylene oxide and 232 parts of propylene oxideare added to 72 parts of the amine mixture described in Example 70. 65parts of the resulting reaction product are reacted with 3.6 parts ofamidosulphonic acid for 6 hours at 100 C. and a product [1 results inthis way.

EXAMPLE 72 768 parts of ethylene oxide are added to 300 parts of theamine mixture described in Example 70. 230 parts of propylene oxide arethen added to 65 parts of the resulting adduct. There is thus obtained aproduct 0.

EXAMPLE 73 232 parts of propylene oxide and then 132 parts of ethyleneoxide are added to 72 parts of the amine mixture described in Example70. 100 parts of the resulting reaction product are reacted with 6.6parts of butylene oxide at 140-170 C. In this way a product d isobtained.

EXAMPLE 74 75.6 parts of ethylene oxide and subsequently 22 parts ofpropylene oxide are added to 117 parts of the product c, so that aproduct e is obtained.

EXAMPLE 75 116 parts of propylene oxide are added to 71 parts of acommercially available addition product of 10 mols of ethylene oxide to1 mol of stearylamine; product f is obtained thereby.

EXAMPLE 76 938 parts of ethylene oxide are added to 20 parts of theamine mixture mentioned in Example 70. 100 parts of the resultingproduct are then reacted with 70.5 parts of butylene oxide. In this waya product g is obtained.

EXAMPLE 77 21 mols of ethylene oxide and 119 mols of propylene oxide areadded to 1 mol of the amine mixture mentioned in Example 70. The endproduct is product It.

EXAMPLE 78 20 mols of propylene oxide and 15 mols of ethylene oxide areadded to 1 mol of the amine mixture mentioned in Example 70. In this waya product i is obtained.

EXAMPLE 79 While stirring well 18 g. of phosphorus pentoxide are addedduring 1 hour at 5060 C. to 100 g. of product i. Subsequently themixture is heated for a further 2 hours at -100 C. In this way product i(1) is obtained.

EXAMPLE 8O 25 ml. of Water are added to 50 g. of the product i (l) andneutralization with a 30% sodium hydroxide solution is effected to givea pH value of 7.0. Subsequently 15 ml. of N sodium hydroxide solutionare added and the mixture is heated for 1 hour at -100 C. Subsequentlyneutralization is effected and the water is removed in a vacuum. In thisway a product i (2) is obtained.

[EXAMPLE '81 2.5 g. of finely pulverized solid sodium hydroxide areadded to 50 g. of the product i. The resulting mixture is stirred forabout 2 hours at 40-50" C. and 2.8 g. of monochloroacetic acid arestirred in slowly thereafter. Stirring is continued for a further hourat 50 C. and subsequently for a further three hours at 75-80 C. In thisway a product i (3) is obtained.

EXAMPLE 82 1 mol of the product i is quaternized in the usual way with1.25 mols of monochloroacetic acid. A product i (4) is obtained.

EXAMPLE 83 Product 1' (5) is a reaction product of 1 mol of the producti with 1.25 mols of maleic acid anhydride.

EXAMPLE 84 Product k is an addition product of 179 mols of propyleneoxide and 21 mols of ethylene oxide to 1 mol of the amine mixturementioned in Example 70.

EXAMPLE 85 5 mols of propylene oxide, then 11 mols of ethylene oxide andfinally 5 mols of propylene oxide are added to 1 mol (415 g.) of acommercially obtainable amine mixture having the following composition:

stearyl-aminopropylamineabout 25% arachinyl-aminopropylamine-about 35%behenyl-aminopropylamine-about 40% In this way a product 1 is obtained.

EXAMPLE 86 25 mols of propylene oxide and 25 mols of ethylene oxide areadded to 1 mol of the amine mixture mentioned in Example 70. In this waya product In is obtained.

IEXAMPLE 87 A product n is an addition product of 25 mols of propyleneoxide and 11 mols of ethylene oxide to 1 mol ofN-dodecyl-aminopropylamine.

EXAMPLE 88 20 mols of propylene oxide, 10 mols of ethylene oxide and 3mols of butylene oxide are added to 1 mol of d-odecylamine. A product isobtained.

EXAMPLE 89 30 mols of propylene oxide and 20 mols of ethylene oxide areadded to 1 mol of N-hexadecylethylenediamine (C H NH-CH CH NH A productp results.

EXAMPLE 90 200 mols in all of propylene oxide and 100 mols in all ofethylene oxide are added to 1 mol of the amine mixture mentioned inExample 70. A product r is obtained.

DYEING EXAMPLES In order to carry out the examples given hereinafter thedyestuffs used correspond to the following formulae, -TCPY signifyingthe trichloropyrimidine residue derived from tetrachloropyrimidine.

Dyestulf A SO3H RH 21H:

S o n IE3 I OH;

I SOQH I S 0 H NH 1H;

8 Dyestuif D Dyestuff E S0311 OH Dyestulf F Dyestuif G 1,2-cobaltcomplex of the sodium salt of 1-2'-hydroxy- 5' nitrophenylazo 2 hydroxy3 tric'hloropyrimidyl- I aminonaphthalene-7,3'-disulphonic acid.

The dyestuif J is obtained by the condensation of 1 mol of copperphthalocyaninetetrasulphonylchloride with 1-2 mol of the followingcompound 9 Dyestuff L N=N' s o ri S 0311 Dyestuff M 1:2-chromium complexof Dyestuff N 1:2-chromium complex of S|O3H EXAMPLE 1 A dyebath isprepared from:

5000 parts of water,

2 parts of the dyestuff A,

parts of sodium sulphate, 3 parts of acetic acid and 1 part of theadjuvant 1.

100 parts of loose wool are entered at 50 C. into the bath, heating tothe boil during the course of 45 minutes is effected and dyeing iscontinued for 1 hour at 95-100 C. A level scarlet red dyeing results.The dyebath then no longer contains any dye. When the adjuvant 1 is notpresent in the dyebath, the dyeing of the wool is not level and,furthermore, the dyestuff has not been absorbed completely on the wool.

When one of the adjuvants 2-30 is added to the dyebath instead of theadjuvant 1, there is obtained likewise a level dyed wool.

EXAMPLE 2 Woollen cloth is dyed at a liquor ratio of 1:40 in a bathcontaining, based on the cloth, 3% of dyestuff B, 1.5% of acetic acid,5% of sodium sulphate and 0.75% of the adjuvant 1. Otherwise dyeing iseffected as stated in Example 1 and a level red dye results. Similarly,level dyeings are obtained when using, instead of the adjuvant l, forexample 1 part of the adjuvant 26, 32, 44 or 53. When the said adjuvantsare not present in the bath, nonlevel dyeings are obtained.

EXAMPLE 3 100 parts of woolen cloth are placed into 4000 parts of a bathcontaining 4 parts of acetic acid, 5 parts of sodium sulphate and 1 partof the adjuvant 31. The woolen cloth is pretreated for minutes at atemperature of 50 C. Thereafter 2 parts of the dyestuff C are added tothe bath. Heating to the boil is effected during 45 minutes and dyeingis subsequently carried out for 1 hour at the boil. A level dyeing isobtained. A level dyeing is also obtained when a similar amount of eachof the adjuvants listed in Table 2 and 3 is present in the bath insteadof the adjuvant 31. In the absence of the said adjuvants non-leveldyeings are obtained.

EXAMPLE 4 Example 3 is repeated with a similar success, but this time,instead of the dyestufi C, dyeing is effected with the same quantity ofdyestuff D.

EXAMPLE 5 Example 3 is repeated, but this time, instead of the dyestuffC, the same amount of dyestuff E is used. A level and full orange dyeingis obtained. In the absence of the adjuvant a skittery dyeing isobtained.

EXAMPLE 6 Dyeing according to Example 3 is repeated but instead of thedyestuff C, 3 parts of the dyestuff F are used. A level blue dyeingresults. In the absence of an adjuvant a strongly skittery dye materialresults.

EXAMPLE 7 100 parts of woollen cloth are placed into 4000 parts of adyebath containing 4 parts of acetic acid, 5 parts of sodium sulphateand 0.5 part of the adjuvant 31. The cloth is placed in the bath at atemperature of 50 C. and pretreated for 10 minutes. At this stage 3parts of the dyestuff G are added and heating to the boil during 45minutes is effected and dyeing is carried out for 1 hour at the boil. Alevel dye of woollen cloth results.

When using, in place of adjuvant 31, the same quantity of each of theadjuvants 3255 a likewise level dyed woollen cloth results. Furthermore,when dyestuff G is replaced with 3 parts of the dyestuft A, a similarlylevel dyed woollen cloth is obtained. Without the presence of theadjuvants mentioned the woollen cloth shows a non-level dyeing.

EXAMPLE 8 Example 3 is repeated, but this time, instead of dyestuff C, 2parts of dyestuff H are added and dyeing is not effected at 100 C., butat temperatures between 78 and 83 C. Level dyed wool is obtained.

EXAMPLE 9 The procedure is as described in Example 3, but the dyestutfmentioned therein is replaced with 3 parts of the dyestuff J. A leveldyeing results.

However, when dyeing is effected in the absence of the adjuvant, thedyeing is non-level.

EXAMPLE 10 Using the dyestuff F a printing paste is prepared having thefollowing composition:

40 parts of dyestuff F,

60 parts of urea,

30 parts of adjuvant 31,

30 parts of acetic acid (40%),

20 parts of turpentine oil,

190 parts of tragacanth thickener 60: 1000 and 630 parts of water.

This printing paste is used for printing by the Vigoureux process onworsted woollen material in the usual way, steaming during 50 minutes iseffected twice, the usual rinsing is effected and finishing carried out.The resulting printed wool has very good fastness properties of whichthere may be mentioned especially acid overdyeing fastness, pottingfastness and fastness to drops of water.

EXAMPLE 1 l parts of woollen yarn are placed in to 4000 parts of adyeing liquor containing 2 parts of acetic acid, 5

11 parts of sodium sulphate and 1 part of adjuvant 32. At a temperatureof 50 C. pretreatment of the Woollen yarn is effected for 20 minutes. 2parts of the dyestuff K are then added to the bath. Heating to the boilis effected during 45 minutes and dyeing at the boil is carried out for1 hour. A level dyeing results. A level dyeing is likewise obtained whenusing, instead of adjuvant 31, similar quantities of each of theadjuvants 32-55.

A level dyed wool is likewise obtained when using, instead of thedyestuff K, 3 parts of the dyestuff L or 5 parts of the dyestuff M fordyeing. Without the presence of the stated adjuvants, the dyeings areclearly not level.

EXAMPLE 12 The procedure is as in Example 11, but the dyestuff K isreplaced with the same amount of the dyestuif N and, instead of woollenyarn the same quantity of woollen cloth is used. Level dyeings result.Without the presence of one of the stated adjuvants the dyeing is notlevel.

When the adjuvants are not present in the dyebath, the dyestuff is onlyincompletely adsorbed.

EXAMPLE 13 A dyebath is prepared from 5000 parts of Water,

2 parts of dyestuff A,

5 parts of sodium sulphate, 3 parts of acetic acid and 1 part of theproduct a.

100 parts of loose wool are added to the bath at 50 C., heating to theboil is effected during 45 minutes and dyeing is continued during 1 hourat 95-100 C. A level scarlet red dyeing results. At that time dyestuffis no longer present in the dyebath. When the product a is not presentin the dyebath, the wool does not become level dyed and the dyestuff,furthermore, is not completely adsorbed onto the wool.

When, instead of the product a, the same amount of each of the productsb, c, d, e. or f is added to the dyebath, wool is obtained which islikewise level dyed.

EXAMPLE 14 Woollen cloth is dyed at a liquor ratio of 1:40 in a bathwhich contains, based on the weight of the cloth, 3% of dyestuff B, 1.5%of acetic acid, 5% sodium sulphate and 0.75% of the product a. Otherwisethe dyeing is effected as stated in Example 1 and a level red dyeing isobtained. Level dyeings are likewise obtained when there is used,instead of the products a, 1 part of each of the products b, c, d or 1.When the said products are not present in the bath, dyeings result whichare not level.

EXAMPLE 15 100 parts of woollen cloth are put into 4000 parts of a bathcontaining 4 parts of acetic acid, 5 parts of sodium sulphate and 1 partof the product a. Pretreatment of the woollen cloth is effected at 50 C.for 20 minutes. 2 parts of dyestuff C are then added to the bath. During45 minutes heating to the boil is effected and subsequently dyeing iscarried out at the boil for 1 hour. A level dyeing results. A leveldyeing is likewise obtained when, instead of the product a, there isused 1.5 parts of each of the products b, c, d, e or f in the bath. -Inthe absence of the said products dyeings are obtained which are notlevel.

lEXAMPLE 16 The procedure of Example 15 is repeated with a similarsuccess, except that the dyestuff C is replaced with the same amount ofthe dyestuff D to effect dyeing.

12 EXAMPLE 17 The procedure of Example 15 is repeated, but the sameamount of dyestuff E is used instead of the dyestuff C. A level and fullorange dyeing results. In the absence of the said adjuvant a skitterydyeing results.

EXAMPLE l8 Dyeing in accordance with Example 15 is repeated but, insteadof dyestuff C, 3 parts of dyestufi F are used. A level blue dyeingresults. In the absence of one of the products a, b, c, d, e and/or 7 avery skittery dyeing on the material results.

EXAMPLE 19 100 parts of woollen cloth are placed into 4000 parts of adyebath containing 4 parts of acetic acid, 5 parts of sodium sulphateand 0.5 part of the product a. The cloth is put into the bath at atemperature of 50 C. and pretreated for 10 minutes. At this time 3 partsof the dyestufi A is added, heating to the boil during 45 minutes iseffected and dyeing is effected for 1 hour at the boil. A level dyedWoollen cloth results. A level dyed Wool also results when adding,instead of the product a, one part of each of the products b, c, d, e,f, g, h, i, il, i2, i3, i4, i5, k, l, m, n, 0, p, q, or r. Furthermore,when the dyestuff G is replaced with 3 parts of the dyestuff A, awoollen cloth is obtained which is likewise level dyed. Without thepresence of the said products the woollen cloth is not level dyed.

EXAMPLE 20 Example 15 is repeated. However, instead of the dyestuff C, 2parts of the dyestuff H are added and dyeing is not effected at -100 C.,but at temperatures between 78 and 83 C. Wool is obtained which isleveldyed.

EXAMPLE 21 The procedure of Example 15 is repeated, but the dyestufftherementioned is replaced with 3 parts of the dyestuff I. A leveldyeing is obtained.

On the other hand, when dyeing is effected in the absence of theadjuvant, the dyeing is not level.

EXAMPLE 22 The procedure of Example 10 is repeated but, instead ofadjuvant 31, the same amount of product a is used; the Vigoureux printobtained in this way had good properties as described in Example 10.

EXAMPLE. 23

Using 1 part of product a, instead of adjuvant 32, the procedure ofExample 11 is repeated; the results obtained are similar to those ofExample 11.

EXAMPLE 24 The procedure is as in Example 13, but the dyestufi K isreplaced with the same quantity of the dyestuff N and, in place of thewoollen yarn, the same amount of woollen cloth is used. Level dyeingsare obtained. Without the presence of the said adjuvant the dyeing isnot level. When the products are not present in the dyebath, thedyestufi is only incompletely adsorbed on to the woollen cloth.

It will be appreciated that among the alkoxylated amines of the FormulaI above are products corresponding to the formula in which R is thehydrocarbon residue of a fatty acid with from.

12 to 24, e.g. 16-22, carbon atoms,

n is an integer from 2 to 3,

m is an integer from 1 to 2,

and each of X, Y and Z represents a polyalkylenoxide residue consistingof some alkylene portions with 2 carbon atoms, the remainder having 3 to4 carbon atoms, with the proviso that the sum of the al kylene portionswith 3 to 4 carbon atoms must be 7 to 200 and that of the ethyleneportions must be 2 to 100 and the further proviso that the sum of allthe al kylene groups in X, Y and Z must be greater than 20,

their reaction products with polybasic acids, salts thereof,quaternization products thereof and etherification products thereof,wherein R is the hydrocarbon residue of a high molecular weight fattyacid of the formula RCOOH, A is a group selected from the classconsisting of Y is selected from. the class consisting of Z is selectedfrom the class consisting of L Jt m is an integer of from 1 to 6,

n is an integer from 2 to 6,

p is selected from 1 and 2,

each of r, s and t independently of one another is an integer of from 1to 200, and

each of x, y and z independently of one another is selected from 2, 3and 4, with the proviso that at least one but not more than 100'ethylene oxide groups and at least one but not more than 200 alkyleneoxide groups with 3 to 4 carbon atoms must be present in the compound ofthe Formula I.

2. A process according to claim 1, in which the colouring is effected inthe presence of a product corresponding to the formula in which R is thehydrocarbon residue of a fatty acid of the for- 14 mula R -COOH whereinR contains from 16 to 22 carbon atoms,

LCIHH OIt H and x, y, z, r, s and t are chosen in such a way that saidproduct contains 11 to 25 ethenoxy and 10 to 25 1,2-propenoxy groups inits molecule.

3. A process according to claim 1, in which the colouring is effected inthe presence of a product corresponding to the formula R CO is theradical of a fatty acid with R containing 16 to 22 carbon atoms each ofthe symbols X Y and Z represents an alkylenoxy residue, all of whichtogether are constituted by from 1 to ethenoxy and from 2 to 1001,2-propenoxy groups and m is selected from 1 and 2.

4. A process according to claim 1, in which the compound of Formula I ispresent in a partially sulphated form. t

5. A process according to claim 1, in which said fibrous material to becoloured with a reactive dye is wool.

6. A process according to claim. 1, in which the amine portion of saidalkoxylated amine is selected from tallamine, aminopropyltallamine,aminoethyltallamine, amines of the formulae 2 ,H in which and dodecyl,tetradecyl-, cety1, stearyl-, oleyl-, arachinyl-, behenylandlignocerylamine.

8. A process according to claim 1, in which the colouring is effected inthe presence of a quaternization product of said alkoxylated amineproduced by means of a 15 16 quaternization agent selected from diethylsulphate, References Cited methyl chloride, benzyl chlo ride, a halogencarboxylic UNITED STATES PATENTS acid, a halogen carboxyhc acld esterand a halogen carboxylic acid amide 7 3,218,116 11/ 1965 Casty et a1.854 9. A process according to claim 1, in which said alk- 5 329'1556'12/1966 Berger '854 ox lated amine contains a luralit of eth lene oxide,pr pylene oxide and butylerfe oxide residues GEORGE LESMES PnmaryExammer 10. A process according to claim 1, in which said fi- T. J.HERBERT, JR., Assistant Examiner brous material of a natural polyamideis coloured by dyeing in a dyebath containing at least one reactive dye10 in the presence of said alkoxylated material. A,

